U.S. patent number 4,021,368 [Application Number 05/542,515] was granted by the patent office on 1977-05-03 for process of treating mycelia of fungi for retention of metals.
This patent grant is currently assigned to Ceskoslovenska komise pro atomovou energii Praha. Invention is credited to Pavel Hulak, Rudolf Jilek, Josef Katzer, Pavel Nemec, Hubert Prochazka, Jiri Stamberg, Karel Stamberg.
United States Patent |
4,021,368 |
Nemec , et al. |
May 3, 1977 |
Process of treating mycelia of fungi for retention of metals
Abstract
Biomasses of mycelia of microorganisms, particularly of fibrous
fungi used for retention of metal ions from solutions, particularly
of uranium, radium, lead and similar are stiffened by adding
polymerizable components to them by polymerization, and the product
is subsequently mechanically granulated. The granulated product is
then employed in cyclically repeated sorption processing of heavy
metal ions by contacting it with solutions of such metals.
Inventors: |
Nemec; Pavel (Bratislava,
CS), Prochazka; Hubert (Brno, CS),
Stamberg; Karel (Prague, CS), Katzer; Josef
(Prague, CS), Stamberg; Jiri (Prague, CS),
Jilek; Rudolf (Brno, CS), Hulak; Pavel (Ceske
Budejovice, CS) |
Assignee: |
Ceskoslovenska komise pro atomovou
energii Praha (Prague, CS)
|
Family
ID: |
26987855 |
Appl.
No.: |
05/542,515 |
Filed: |
January 20, 1975 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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331659 |
Feb 12, 1973 |
|
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|
Current U.S.
Class: |
210/688; 423/6;
502/402; 502/404; 435/256.3; 435/256.8; 423/DIG.17; 502/7;
502/403 |
Current CPC
Class: |
C02F
1/286 (20130101); C12N 1/005 (20130101); G21F
9/12 (20130101); C02F 3/34 (20130101); B01J
20/22 (20130101); C22B 3/18 (20130101); B01J
20/24 (20130101); B01D 15/00 (20130101); Y10S
423/17 (20130101); Y02P 10/234 (20151101); Y02P
10/20 (20151101); C02F 2101/006 (20130101) |
Current International
Class: |
B01J
20/22 (20060101); B01J 20/24 (20060101); B01D
15/00 (20060101); C02F 1/28 (20060101); C02F
3/34 (20060101); C12N 1/00 (20060101); C22B
3/00 (20060101); C22B 3/18 (20060101); G21F
9/12 (20060101); B01D 015/00 (); C02B 001/14 () |
Field of
Search: |
;195/1,28R,81,52,53,54,55,56 ;210/38B,503,504 ;252/427 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Tanenholtz; Alvin E.
Parent Case Text
This application is a continuation-in-part of application Ser. No.
331,659, filed on Feb. 12, 1973 and now abandoned.
Claims
What is claimed is:
1. A process of treating as biomass the mycelia of microorganisms
to produce a stiffened essentially water-insoluble granulated
product for application for the industrial retention from solutions
of heavy metal ions chosen from the group consisting of uranium,
radium, and lead by cyclically repeated sorption processing of such
heavy metal ions by contacting it with solutions of such metal
ions, comprising mixing the biomass with at least one polymerizable
stiffening component capable of forming a polymeric system in a
weight ratio of 1 part biomass to 0.1 - 3 parts stiffening
component, polymerizing the biomass and stiffening component
mixture to produce a stiffened essentially water-insoluble product,
drying the stiffened product, the polymerizing and drying steps
being carried out at a temperature of about 90.degree. -
105.degree. C. and granulating the resulting dried stiffened
product.
2. A process as in claim 1, comprising employing the granulated
stiffened product in cyclically repeated sorption processing of
heavy metal ions by contacting it with solutions of such metal
ions.
3. A process as in claim 2, wherein the polymerizable stiffening
component is chosen from the group consisting of formaldehyde,
resorcinol, urea, m-phenyldiamine, gelatine, starch, bone glue,
casein, epoxide resin and acrylic resin.
4. A process as in claim 3, wherein the acrylic resin is chosen
from the group consisting of polyglycol methacrylates,
polyacrylamides, polymethacrylamides and copolymers thereof.
5. A process as in claim 2, wherein the mycelia of microorganisms
are of the fibrous fungi of the strain Penicillium Aspergillus.
6. A process as in claim 5, wherein the mycelia of microorganisms
is in the natural condition.
7. A process as in claim 5, wherein the mycelia of microorganisms
is in a dry condition.
Description
BACKGROUND OF THE INVENTION
This invention relates to a process of a chemical and physical
treatment of a mycelium which is in a natural or dry condition or
has been treated by crushing, and to a process of treating
solutions of heavy metals thereby. The mycelium may belong to
different kinds of microorganisms, particularly of fibrous fungi
capable of retention of metals such as uranium, lead, radium and
others from their solutions. The retention mechanism may be for
instance based on sorption.
It has already been proposed to apply the mycelium of some kind of
lower fungi, advantageously of waste mycelium in the fermenting and
pharmaceutical industry for removal of uranium, of elements of the
uranium-radium type, of lead and other metals. This material has a
good capacity and selectivity but has a drawback in having a low
mechanical rigidity; this causes difficulties in the retention or
sorption process by means of a column or by other modifications of
dynamic sorption in industrial operation. This holds true for both
for filtered native mycelium and for dried mycelium.
SUMMARY OF THE INVENTION
We have found that this drawback can be eliminated by a suitable
stiffening of the supporting skeleton of the mycelium which is
predominantly composed of polymers of the polysaccharide type.
According to this invention, the mycelium is stiffened by suitable
chemical adjustment, particularly by the cross-linking of its
macromolecular structure, by stiffening by high molecular material
or by both methods simultaneously.
In a convenient arrangement of this adjustment, the active centers
capable of selectively bonding with above mentioned heavy metal
ions remain practically untouched, in the original mycelium,
resulting in the maintenance of their capacity and of other
sorption properties.
The method of chemical adjustment has to be chosen so as to
correspond to the chemical structure of the mycelia, that is, to
their polysaccharide and polypeptide components. It is possible to
use as polymerizable components formaldehyde and further
monofunctional aldehydes, glyoxal, glutaraldehyde, or other
polyfunctional aldehydes, for instance, a solution of
polyacroleines in sulphurous acid. Similar results are obtained
with diisocyanates, or with epichlorhydrine, dichlorhydrines,
chlorides of dicarboxyl acids and others. Improvements in the
mechanical properties of the mycelium can be also obtained by
application of natural or artificial pickling agents, for instance,
by polyvalent phenols or by chromium salts.
Furthermore, a number of natural high molecular materials can be
used for stiffening of the mycelium. Gelatine can, for instance, be
used from the polypeptides. It can be applied in the form of
aqueous solutions and is subsequently cured by formaldehyde.
Similarly, it is possible to apply casein (for instance dissolved
in lye), different glues, zein, albimin and other polypeptidic
materials. From the polysaccharides starch or its hydrolytic
products in aqueous solutions or cellulose (dissolved for instance
in Schweitzer's agent can be used, or as xantogenate) which can be
subsequently stiffened by the action of diisocyanates,
epoxycompounds, dialdehydes, chlorides of dicarboxyl acids and
similar. From starch derivatives there can be used, for instance,
its oxidized form with aldehydic groups. Other advantageous natural
materials are also pectins, gums, and slimes (arabic gum, agaragar
and others), dextrates, lignin, or its derivatives.
Synthetic materials capable of forming high molecular structures,
advantageously having hydrophylic properties, are equally suitable
for the stiffening of mycelia. These particularly include phenols,
amines, or their derivatives, multivalent phenols and amines, or
derived compositions also containing carboxyl groups. It is also
possible to "saturate" the mycelia by these materials and start
their polycondensation by an addition of formaldehyde. Other
monofunction or polyfunction aldehydes (such as acetaldehyde,
glyoxal, glutaraldehyde and others) urotropin, diisocyanates,
epoxide compositions and others can be used besides formaldehyde.
Hydrophilic groups (sulphon, amine groups) can be introduced into
the structure also in the course of the polycondensation, for
instance by sulphomethylation or aminoethylation. Urea is also
suitable in addition to amines and phenols, or methylureas,
thiourea, melanin, dicyandiamide, guanidin and their derivatives.
Another suitable material is plyvinylacetate hydrolized to a
different degree, or completely hydrolyzed to polyvinylalcohol. (In
order to increase the insolubility, tempering can be applied by the
action of phosphoric acid, diisocyanates, chlorides or anhydrides
of polycarboxylic acid, polyaldehydes, trimethylpropane and
similar. Another group of materials suitable for stiffening mycelia
are acrylic acid, methacrylic acid, their esters (for instance
glycolmethacrylate, glycidylmethacrylate and similar), amides,
nitriles and similar materials. These monomers are mixed in order
to increase the insolubility with polyvinyl components such as
divinylbenzene, ethyldimetacrylate and similar, or the finished
polymers are cross-linked additionally, for instance, by the action
of formaldehyde or polyacrylamide. A suitable stiffening component
is also ethylenimin, or polyethylenimin combined, for instance,
with polyaldehydes. Other groups of materials suitable for
stiffening of mycelia are polyurethanes, polyureas and epoxides
resins.
EXAMPLES OF THE PROCESS
EXAMPLE 1
8 g of dried mycelium of the strain Penicillium chrysogenum was
mixed with 4.9 ml of water, 0.1 g sodium hydroxide and 3.54 ml of
35% formaldehyde was added and boiled under a reflux condenser for
1 hour. After cooling, a solution containing 2 g of resorcinol, 4.9
ml of water and 3.54 ml of 35% formyldehyde was added. The mixture
was left standing after mixing at simultaneous heating to
70.degree. C. It was thereafter heated under continuous mixing to
80.degree. C whereby condensation proceeded to a dull red liquid,
which condensed fully in a drying chamber at a temperature of
105.degree. C. The product was crushed to a grain size of 0.3 to
0.75 mm. The capacity of the sorbent for uranium was 95.7 mg/g.
(The capacity for uranium was determined by a static method in all
mentioned examples as follows: 1 g of the sorbent was shaken for 16
hours with 100 ml of a solution UO.sub.2 (NO.sub.3).sub.2 having a
concentration of uranium of 1 g/l, the capacity being calculated
from the decrease of uranium in the solution).
EXAMPLE 2
4 g of dried mycelium of the strain P chrysogenum was mixed with a
solution containing 5 ml water, 0.08 sodium hydroxide and 3.6 ml
formaldehyde and boiled under a reflux condenser for 11/2 hour.
Then 0.5 ml concentrated hydrochloric acid was added slowly, cooled
down and the obtained precondensate triturated in a dish. It was
subsequently rinsed by 3.6 ml of 35% formaldehyde into a dish and
under effective cooling a solution of 2 g m-phenylendiamine in 5 ml
water acidified by 1.65 ml of hydrochloric acid was added at once.
The condensation took place in the course of about 45 seconds at
creation of red-brown liquid, which condensed fully in a drying
chamber at 105.degree. C. The product was crushed to a grain size
of 0.3 to 0.75 mm.
The capacity of the sorbent for uranium was 39.3 mg/g.
EXAMPLE 3
6.9 g of urea was dissolved in 30 ml water and 15 g 35%
formaldehyde was added with the pH value adjusted to 7.5 by a
sodium lye. 27.6 g of mycelium P chrysogenium in crushed shape was
added and the whole was heated in an aqueous bath for about 2
hours. After transfer to a porcelain dish, 2 ml of concentrated
acetic acid was added into the precondensate and the final
condensation proceeded in a drying chamber at a temperature of
90.degree. to 105.degree. C. in the course of 2 to 21/2 hours. The
product was crushed to a grain size of 0.3 to 0.75 mm.
The capacity of the sorbent for uranium was 92.1 mg/g.
EXAMPLE 4
5 g of a precondensate of an epoxide resin having the commercial
designation Epoxy 1200 was mixed with 10 g of a curing agent of the
commercial design P1. The originating paste-like suspension was
converted to a solution by 10 ml of acetone, with which 25 g of
mycelium P chrysogenium, prior prepared to a grain size about 0.3
to 0.5 mm was impregnated. The acetone was distilled away by
heating, and the curing was finished in a drying chamber at a
temperature of 100.degree. C. The individual particles from a
compact highly porous block, which is crushed relatively easily to
the original grain size. (The grain size is eventually adjusted by
shifting). The capacity of the sorbent for uranium is 94.1
mg/g.
EXAMPLE 5
15 g of finely crushed mycelium of the strain P chrysogenum was
mixed in a tritutated dish with 10 ml of water and 10 g
polyvinylacetate emulsion (content in the dry form was 54.8 % ). A
mass of paste-like consistency was thus created, which was
perfectly homogenized by a pestle and subsequently cured in a
drying chamber at a temperature of about 100.degree. C. The product
was crushed to a grain size of 0.3 to 0.75 mm.
Capacity of the sorbent for uranium was 69.4 mg/g.
EXAMPLE 6
5 g of gelatine was dissolved in 30 ml water (by beating in an
aqueous bath) and 15 g moistened, finely triturated mycelium of the
strain P chrysogenum was added. A mass of paste-like consistency
was obtained, which was perfectly homogenized and kneaded in a
trituration dish. 5 ml of 35% formaldehyde was subsequently added
and again kneaded. The curing was performed in a drying chamber at
a temperature of about 100.degree. C. The hardened product was
crushed and sifted to a grain size of 0.3 to 0.75 mm.
The capacity of the sorbent for uranium was 100.9 mg/g.
EXAMPLE 7
4 g of bone glue was dissolved in 30 ml of heated water and 16 g of
mycelium of the strain P chrysogenum was added to the solution.
After perfect homogenizing in a trituration dish, 5 ml of 35%
formaldehyde was added, the mixture was kneaded, and was cured in a
drying chamber at a temperature of about 100.degree. C. The product
was crushed to a grain size of 0.3 to 0.75 mm.
The capacity of the sorbent for uranium was 102.5 mg/g.
EXAMPLE 8
5 g of wheat starch was mixed with 10 ml of water at room
temperature, then poured into 20 ml of boiling water. The created
starch paste was "triturated" with 15 g of finely triturated
mycelium of the strain P chrysogenum, which has to be moistened
prior to introduction into the starch paste. The mass of paste-like
consistency was cured in a drying chamber for about 10 hours at a
temperature of 90.degree. to 100.degree. C. The product was crushed
to a grain size of 0.3 to 0.75 mm.
The capacity of the sorbent for uranium was 88.9 mg/g.
EXAMPLE 9
5 g of casein was rinsed with 10 ml of water, left about 1/2 hour
to swell, then 15 g of finely crushed and moistened mycelium of the
strain P chrysogenum and 5 ml of 35% formaldehyde were added and
everything was perfectly homogenized in a trituration dish. The
mixture gradually thickened to a homogeneous thick paste. The
curing was finished in a drying chamber at a temperature of
100.degree. C. The product was crushed to a grain size of 0.3 to
0.75 mm. The capacity of the sorbent for uranium was 92 mg/g.
EXAMPLE 10
30 g of mycelium of the strain P chrysogenum was introduced into
150 ml of 35% formaldehyde, to which has been prior added 1.5 g
sodium hydrozide. (The mycelium had been adjusted to a grain size
of 2 to 3 mm). The mixture was maintained boiling in a flask with a
reflux condenser for about 2 hours. Then the liquid phase was
decanted and the solid phase washed on a filter with water. The
curing was finished in a drying chamber at a temperature of about
100.degree. C. The grain size of the product was adjusted to 0.3 to
0.75mm.
The capacity of the sorbent for uranium was 98.5 mm/g.
When polymerization is mentioned in the specification or claims,
this term is intended to include not only polymerization on double
bonds, but also any other reaction by which polymers originate from
low molecular starting material, such as polycondensation,
polyaddition, and similar actions.
Under the term "native" such a state of mycelium is to be
understood which is characteristic for the cultivation, growth and
the like stage thereof, which means that mycelium in a fermentor
(or immediately withdrawn therefrom) can be called as native
mycelium, in contradistinction to dried mycelium in which all the
biological and biochemical processes have been interrupted and
finished.
The term "biomass" is to be understood as a generic term for
mycelium, i.e. both native and dried mycelium; the composition of
biomass is characterized or influenced by the conditions of
preparing the same, such as, for instance, cultivation period,
temperature, composition of nutrients medium, temperature and
method of drying, etc.
Although the invention is illustrated and described with reference
to a plurality of preferred embodiments thereof, it is in no way
limited to the disclosure of such a plurality of preferred
embodiments thereof, but is capable of numerous modifications
within the scope of the appended claims.
* * * * *